Open-chain alkoxyamines and their corresponding nitroxides for controlled low temperature radical polymerization

ABSTRACT

The present invention relates to open chain alkoxyamine compounds, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) at least one open chain alkoxyamine compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of open chain alkoxyamine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator X, as well as a process and their use for polymerization are also subjects of the present invention.

The present invention relates to open chain alkoxyamine compounds, apolymerizable composition comprising a) at least one ethylenicallyunsaturated monomer and b) at least one open chain alkoxyamine compound.Further aspects of the present invention are a process for polymerizingethylenically unsaturated monomers, and the use of open chainalkoxyamine compounds for controlled polymerization. The intermediateN-oxyl derivatives, a composition of the N-oxyl derivatives withethylenically unsaturated monomers and a free radical initiator X., aswell as a process and their use for polymerization are also subjects ofthe present invention.

The compounds of the present invention provide polymeric resin productshaving low polydispersity. The polymerization process proceeds withenhanced monomer to polymer conversion efficiency at low temperatures.In particular, this invention relates to stable free radical-mediatedpolymerization processes which provide homopolymers, random copolymers,block copolymers, multiblock copolymers, graft copolymers and the like,at enhanced rates of polymerization and enhanced monomer to polymerconversions at low temperatures.

The polymerization processes and resin products of the present inventionare useful in many applications, including a variety of specialtyapplications, such as for the preparation of block copolymers which areuseful as compatibilizing agents for polymer blends, or dispersingagents for coating systems or for the preparation of narrow molecularweight resins or oligomers for use in coating technologies andthermoplastic films or as toner resins and liquid immersion developmentink resins or ink additives used for electrophotographic imagingprocesses.

There are numerous documents in the literature describing the controlledradical polymerization of ethylenically unsaturated monomers usingalkoxyamines or nitroxides.

U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986,discloses a free radical polymerization process which controls thegrowth of polymer chains to produce short chain or oligomerichomopolymers and copolymers, including block and graft copolymers. Theprocess employs an initiator having the formula (in part) R′R″N—O—X,where X is a free radical species capable of polymerizing unsaturatedmonomers. The reactions typically have low conversion rates.Specifically mentioned radical R′R″N—O. groups are derived from 1,1,3,3tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine ordi-t-butylamine. However, the suggested compounds do not fulfill allrequirements. Particularly the polymerization of acrylates does notproceed fast enough and/or the monomer to polymer conversion is not ashigh as desired.

Recently other attempts to develop new polymerization regulators havebeen published. WO 98/4408 and WO 98/30601 disclose heterocycliccompounds suitable for controlled polymerization processes. WO 98/13392discloses open chain alkoxyamines which are derived from NO gas or fromnitroso compounds.

WO 00/07981 discloses a variety of open chain alkoxyamine compounds,which have no or at most only one electron withdrawing group at theC-atom in β-position to the nitrogen atom. These compounds are stable atlow temperature and decompose readily at elevated temperature.

Surprisingly, it has now been found that higher alkyl and phenylsubstitution patterns at the carbon atom in α position to the nitrogenatom lead to initiators/regulators, which allow controlled radicalpolymerization at a temperature of 100° C. or below. Due to the highersteric hindrance around the nitrogen atom, compared to prior artcompounds, high conversions are achievable even at temperatures as lowas 100° C. This makes the compounds particularly useful for controlledradical polymerization processes under aqueous conditions at ambientpressure. So far there exists no regulator/initiator which would allowefficient radical polymerization under such conditions, Polymerizationof monomers with the instant compounds results in a polymer or copolymerof narrow polydispersity and high monomer to polymer conversion even attemperatures below 100° C. High conversions are achieved even in shortreaction times.

One subject of the invention is a compound of formula Ia, Ib, or Ic

wherein

-   Y is O or NR₁₀₁ and R₁₀₁ is H or C₁-C₁₈alkyl or R₇ and/or R₈ and    R₁₀₁ together with the nitrogen atom to which they are bound form a    5 or 6 membered heterocyclic ring;-   R₁, R₂ and R₃ independently are benzyl, C₁-C₁₈alkyl, C₂-C₁₈alkenyl    which are unsubstituted or substituted by OH or a by group    —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by at least one O    atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl;-   or R₁ and R₂ together with the carbon atom to which they are bound    form a C₅-C₁₂cycloalkyl group; or in formula Ia R₃ and R₄ together    with the carbon atom to which they are bound form a C₅-C₁₂cycloalkyl    group;-   R₄ is C₂-C₁₂alkyl;-   R₅ and R₆ are independently H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, benzyl,    C₅-C₁₂cycloalkyl or phenyl;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl, —C(O)—C(O)—OH, —C(O)    —C(O)—NH—(C₁-C₁₈alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₅ are the following group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen; R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ independentlyare H, OH, C₁-C₈alkoxy, C₁-C₈ alkyl, SH, C₁-C₈alkylthio,—O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl, nitro, cyano, halogen or agroup NR₁₀₆R₁₀₇ wherein R₁₀₆ and R₁₀₇ independently are hydrogen,C₁-C₁₈alkyl or C₆-C₁₀aryl or together with the nitrogen atom to whichthey are bound form a 5 or 6 membered heterocyclic ring; and

-   X is selected from the group consisting of-   —CH₂-aryl,

—CH₂—CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl, (C₁-C₁₂)alkyl-CR₂₀—C(O)—O—R₂₁,(C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

3-cyclohexenyl, 3-cyclopentenyl,

wherein

-   R₂₀ is hydrogen or C₁-C₁₂alkyl;-   R₂₁ is C₁-C₁₈alkyl or C₂-C₁₈alkyl which is interrupted by at least    one O atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl;-   the alkyl groups are unsubstituted or substituted with one or more    —OH, —COOH, —O(C₁-C₈alkyl), NR₁₀₆R₁₀₇ or —COR₂₀ groups wherein R₂₀,    R₁₀₆ and R₁₀₇ have the meanings as defined above; the aryl groups    are phenyl or naphthyl which are unsubstituted or substituted with    C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylthio,    C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, SH, —COOH or    —COO(C₁-C₁₂)alkyl.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl with 2 to 18 carbon atoms is a linear or branched radical as forexample vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl oder n-4-octadecenyl.

Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 6carbon atoms.

5 or 6 membered heterocyclic rings are for example piperidine orpyrolidine.

Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butylor hydroxy hexyl.

C₂-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃— or —CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃—. It is preferably derived from polyethlene glycol. A generaldescription is —((CH₂)_(a)—O)_(b)—H/CH₃, wherein a is a number from 1 to6 and b is a number from 2 to 10.

C₂-C₁₈alkyl interrupted by at least one NR₅ group may be generallydescribed as —((CH₂)_(a)—NR₅)_(b)—H/CH₃, wherein a, b and R₅ are asdefined above.

C₆-C₁₀ aryl is for example phenyl or naphthyl, but also comprised areC₁-C₄alkyl substituted phenyl, C₁-C₄alkoxy substituted phenyl, hydroxy,halogen or nitro substituted phenyl. Examples for alkyl substitutedphenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene orisopropylbenzene. Halogen substituted phenyl is for exampledichlorobenzene or bromotoluene.

C₅-C₁₂cycloalkyl is typically cyclopentyl, methylcyclopentyl,dimethylcyclopentyl, cyclohexyl, methylcyclohexyl ortrimethylcyclohexyl.

Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy andtheir corresponding isomers.

The alkythio substituents may be derived from the corresponding alkoxysubstituents already mentioned.

Halogen is fluoro, chloro, bromo or iodo.

Preferably X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₈alkyl)CR₂₀—C(O)-phenyl,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈) alkoxy,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—N-di(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—NH(C₁-C₈)alkyl and (C₁-C₈)alkyl-CR₂₀—C(O)—NH₂,wherein

-   R₂₀ is hydrogen or (C₁-C₈)alkyl.

More preferably X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl and(C₁-C₄)alkyl-CR₂₀—C(O)—NH₂, wherein

-   R₂₀ is hydrogen or (C₁-C₄)alkyl.

Preferably in the compounds of formula Ia, Ib and Ic Y is O and informula Ia R₄ is C₂-C₆alkyl or R₃ and R₄ together with the carbon atomto which they are bound form a 5 to 7 membered cycloalkyl ring.

A preferred subgenus of compounds is wherein

-   R₁, R₂ and R₃ are C₁-C₅alkyl; or in formula Ia R₃ and R₄ together    with the carbon atom to which they are bound form a C₅-C₆cycloalkyl    group; or-   R₄ is C₂-C₆alkyl;-   R₅ and R₆ are H;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, allyl, benzyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—C(O)—OH, —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₈ are the following group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen, C₁-C₈alkyl;

-   R₉, R₁₀ and R₁₁, independently are H, C₁-C₈alkoxy, C₁-C₈alkylthio,    —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen or C₁-C₈alkyl; and-   X is as defined above.

More preferred is a compound of formula Ib or Ic.

A particularly preferred subgenus is a compound of formula Ib wherein

-   Y is O;-   R₁ and R₂ are C₁-C₅alkyl, or together with the carbon atom to which    they are bound form a C₅-C₇cycloalkyl group;-   R₃ is methyl, ethyl or propyl;-   R₅ and R₆ are H;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, allyl, benzyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—C(O)—OH, —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₈ are the following group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen, C₁-C₈alkyl;

-   R₉, R₁₀ and R₁₁ independently are H, C₁-C₈alkoxy, C₁-C₈alkylthio,    —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen or C₁-C₈alkyl; and-   X is selected from the group consisting of-   —CH₂ aryl,

—CH₂—CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl, (C₁-C₁₂)alkyl-CR₂₀—C(O)—O—R₂₁,(C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

3-cyclohexenyl, 3-cyclopentenyl,

wherein

-   R₂₀ is hydrogen or C₁-C₁₂alkyl;-   R₂₁ is C₁-C₁₈alkyl or C₂-C₁₈alkyl which is interrupted by at least    one O atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl;-   the alkyl groups are unsubstituted or substituted with one or more    —OH, —COOH, —O(C₁-C₈alkyl), NR₁₀₆R₁₀₇ or —COR₂₀ groups wherein R₂₀,    R₁₀₆ and R₁₀₇ have the meanings as defined above;-   the aryl groups are phenyl or naphthyl which are unsubstituted or    substituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,    C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C₁-C₁₂)alkyl.

A further subject of the invention is a polymerizable composition,comprising

-   a) at least one ethylenically unsaturated monomer or oligomer, and-   b) a compound according to formula (Ia) (Ib) or (Ic).

Yet another subject of the invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block or random) byfree radical polymerization of at least one ethylenically unsaturatedmonomer or oligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formula(Ia), (Ib) or (Ic) under reaction conditions capable of effectingscission of the O—X bond to form two free radicals, the radical •X beingcapable of initiating polymerization.

Preferably the scission of the O—X bond is effected by ultrasonictreatment, heating or exposure to electromagnetic radiation, rangingfrom γ to microwaves.

More preferably the scission of the O—X bond is effected by heating andtakes place at a temperature of between 50° C. and 160° C., inparticular between 60° C. and 120° C. and most preferred between 80° C.and 100° C.

Preferably the compound of formula Ia, lb or Ic is present in an amountof from 0.001 mol-% to 20 mol-%, more preferably of from 0.002 mol-% to10 mol-% and most preferably of from 0.005 mol-% to 5 mol-% based on themonomer or monomer mixture.

When monomer mixtures are used the average molecular weight is taken asbasis.

Definitions and preferences for the compounds are mentioned above, theyapply also for the composition and process.

Preferably the ethylenically unsaturated monomer is selected from thegroup consisting of ethylene, propylene, n-butylene, i-butylene,styrene, substituted styrene, conjugated dienes, acrolein, vinylacetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

Preferably the ethylenically unsaturated monomer is a compound offormula CH₂═C(R_(a))—(C═Z)-R_(b), wherein R_(a) is hydrogen orC₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₆alkoxy,C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, orhydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;

-   An⁻ is a anion of a monovalent organic or inorganic acid;-   Me is a monovalent metal atom or the ammonium ion.-   Z is oxygen or sulfur.

Examples of acids from which the anion An⁻ is derived areC₁-C₁₂carboxylic acids, organic sulfonic acids such as CF₃SO₃H orCH₃SO₃H, mineralic acids such as HCl, HBr or HI, oxo acids such as HClO₄or complex acids such as HPF₆ or HBF₄.

-   Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O    atom are of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

An⁻, wherein An⁻ and R_(a) have the meaning as defined above and R₈ ismethyl or benzyl. An⁻ is preferably Cl⁻, Br⁻or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

-   Z is oxygen.

More preferred the ethylenically unsaturated monomer is an acrylic acidester, acrylamide, acrylnitrile, methacrylic acid ester, methacrylamide,methacrylnitrile.

Acrylic acid esters and methacrylic acid esters are typicallyC₁-C₁₈alkyl esters.

Most preferred is n-butylacrylate, tert-butylacrylate, methylacrylate,ethylacrylate, propylacrylate, hexylacrylate and hydroxyethylacrylate.

After the polymerization step is completed the reaction mixture may becooled down to a temperature below 60° C., preferably to roomtemperature. The polymer may be stored at this temperature withoutfurther reactions occurring.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

When acrylic or methacrylic monomers are polymerized, the process ispreferably carried out in the presence of an organic solvent. Theconcentration of the monomer in the organic solvent may influencepolymerization rate and final conversion. The concentration may, forexample, vary from 5% to 80% by weight, based on the solvent. It is notnecessary that the whole amount of monomer is present at the beginningof the polymerization. It is also possible to add further monomer afterthe polymerization reaction has already started.

As already mentioned the present compounds are particularly useful foraqueous polymerizations, since they allow efficient conversions attemperatures at or below 100° C.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The process is particularly useful for the preparation of blockcopolymers.

Block copolymers are, for example, block copolymers of polystyrene andpolyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are useful as adhesives or ascompatibilizers for polymer blends or as polymer toughening agents.Poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers)are useful as dispersing agents for coating systeme, as coatingadditives (e.g. rheological agents, compatibilizers, reactive diluents)or as resin component in coatings (e.g. high solid paints). Blockcopolymers of styrene, (meth)acrylates and/or acrylonitrile are usefulas modifiers for plastics, elastomers and adhesives.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends.

The (co)polymers of the present invention may have a number averagemolecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol. Thenumber average molecular weight may be determined by size exclusionchromatography (SEC), matrix assisted laser desorption/ionization massspectrometry (MALDI-MS) or, if the initiator carries a group which canbe easily distinguished from the monomer(s), by NMR spectroscopy orother conventional methods.

The polymers or copolymers of the present invention have preferably apolydispersity of from 1.1 to 2, more preferably of from 1.1 to 1.8 andmost preferably from 1.1 to 1.6.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranched and dendriticcopolymers, as well as graft copolymers.

The polymers prepared by the present invention are useful for followingapplications: adhesives, detergents, dispersants, emulsifiers,surfactants, defoamers, adhesion promoters, corrosion inhibitors,viscosity improvers, lubricants, rheology modifiers, thickeners,crosslinkers, paper treatment, water treatment, electronic materials,paints, coatings, photography, ink materials, imaging materials,superabsorbants, cosmetics, hair products, preservatives, biocidematerials or modifiers for asphalt, leather, textiles, ceramics andwood.

Alternatively controlled free radical polymerization may be carried outusing the nitroxyl precursors of the corresponding alkoxyamines togetherwith a source of free radicals. Consequently a further subject of theinvention is a polymerizable composition, comprising

-   a) at least one ethylenically unsaturated monomer or oligomer, and-   b) a compound according to formula (IIa) (IIb) or (IIc)

wherein

-   Y is O or NR₁₀₁ and R₁₀₁ is H or C₁-C₁₈alkyl or R₇ and/or R₈ and    R₁₀₁, together with the nitrogen atom to which they are bound form a    5 or 6 membered heterocyclic ring;-   R₁, R₂ and R₃ independently are benzyl, C₁-C₁₈alkyl, C₂-C₁₈alkenyl    which are unsubstituted or substituted by OH or a by group    —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by at least one O    atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl; or R₁ and R₂ together with the carbon atom to which they    are bound form a C₅-C₁₂cycloalkyl group; or in formula Ia R₃ and R₄    together with the carbon atom to which they are bound form-   a C₅-C₁₂cycloalkyl group;-   R₄ is C₂-C₁₂alkyl;-   R₅ and R₆ are independently H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, benzyl,    C₅-C₁₂cycloalkyl or phenyl;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl, —C(O)—C(O)—OH, —C(O)    —C(O)—NH—(C₁-C₁₈alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₈ are the following group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen;

-   R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ independently are H, OH, C₁-C₈alkoxy,    C₁-C₈alkyl, SH, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl,    —O—C(O)—(C₆-C₁₀)aryl, nitro, cyano, halogen or a group NR₁₀₆R₁₀₇    wherein R₁₀₆ and R₁₀₇ independently are hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl or together with the nitrogen atom to which they are    bound form a 5 or 6 membered heterocyclic ring; and-   c) a source of free radicals capable of initiating polymerization of    ethylenically unsaturated monomers.

Also subject of the invention is a process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturatedmonomer/oligomer, which comprises subjecting the above composition toheat or actinic radiation.

For example the polymerization is carried out by applying heat and takesplace at a temperature of between 50° C. and 160° C., in particularbetween 60° C. and 120° C. and most preferred between 80° C. and 100° C.

The free radical initiator of component c) is preferably a bis-azocompound, a peroxide perester or a hydroperoxide.

Specific preferred radical sources are 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methyl-butyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide;acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate,t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoylperoxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide,bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetylperoxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α, α′-bis(t-butylperoxyisopropyl) benzene, 3,5-bis (t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

Azo initiators and peroxides are most preferred.

Preferably the nitroxyl radical, component b), is present in an amountof from 0.001 mol-% to 20 mol-%, more preferably of from 0.002 mol-% to10 mol-% and most preferably of from 0.005 mol-% to 5 mol-% based on themonomer or monomer mixture.

Preferably the free radical initiator, component c), is present in anamount of from 0.001 mol-% to 20 mol-%, more preferably of from 0.002mol-% to 10 mol-% and most preferably of from 0.005 mol-% to 5 mol-%,based on the monomer or monomer mixture.

The molar ratio of free radical initiator to stable free nitroxylradical is preferably from 20:1 to 1:2, more preferably from 10:1 to1:2.

The compounds of formula IIb are novel and therefore also subject of thepresent invention

wherein

-   Y is O or NR₁₀₁ and R₁₀₁ is H or C₁-C₁₈alkyl or R₇ and R₁₁₀ together    with the nitrogen atom to which they are bound form a 5 or 6    membered heterocyclic ring;-   R₁, R₂ and R₃ independently are benzyl, C₁-C₁₈alkyl, C₂-C₁₈alkenyl    which are unsubstituted or substituted by OH or a group    —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by at least one O    atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or    C₆-C₁₀aryl;-   or R₁ and R₂ together with the carbon atom to which they are bound    form a C₅-C₁₂cycloalkyl group;-   R₅ and R₆ are independently H, C₂-C₁₈alkyl, C₂-C₁₈alkenyl, benzyl,    C₅-C₁₂cycloalkyl or phenyl;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl, —C(O)—C(O)—OH, —C(O)    —C(O)—NH—(C₁-C₁₅alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₈ are one of the following groups

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen;

-   R₉, R₁₀ and R₁₁ independently are H, OH, C₁-C₈alkoxy, C₁-C₈alkyl,    SH, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,    nitro, cyano, halogen or a group NR₁₀₆R₁₀₇ wherein R₁₀₆ and R₁₀₇    independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl or together    with the nitrogen atom to which they are bound form a 5 or 6    membered heterocyclic ring.

Preferred is a compound of formula IIb wherein

-   Y is O;-   R₁ and R₂ are —CH₃, or together with the carbon atom to which they    are bound form a C₅-C₇cycloalkyl group;-   R₃ is methyl, ethyl or propyl;-   R₅ and R₆ are H;-   R₇ and R₈ independently are H, C₁-C₁₈alkyl, allyl, benzyl,    C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl,    —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—C(O)—OH, —C(S)—S—(C₁-C₁₈)alkyl,

—SiR_(a)R_(b)R_(c) wherein R_(a), R_(b), R_(c) independently areC₁-C₁₈alkyl or R₇ and R₈ are one of the following groups

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen, C₁-C₈alkyl;and

-   R₉, R₁₀ and R₁₁ independently are H, C₁-C₈alkoxy, C₁-C₈alkylthio,    —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen or C₁-C₈alkyl.

Further subjects of the invention are the use of a compound of formulaIa, Ib, or Ic for the polymerization of ethylenically unsaturatedmonomers; the use of a compound of formula IIa, IIb or IIc together witha source of free radicals for the polymerization of ethylenicallyunsaturated monomers and a polymer or copolymer obtainable by one of theabove mentioned polymerization processes.

The definitions and preferences given for the alkoxyamine compoundsapply also for the nitroxyl compounds, their composition withethylenically unsaturated monomers and the polymerization processtherewith.

Open chain alkoxyamines and nitroxides are prepared via two generalroutes.

-   -   A) Oxidation of 3,3,5,5-tetrasubstituted morpholin-2-ones by        peracetic acid, followed by alkylation of the resulting N-oxyls        (CuBr, t-BuOOH, ethylbenzene; or CuCl,        pentamethylethylenetriamine, 1-phenethylbromide) and reductive        ring cleavage (LiAlH₄).    -   B) Ring opening of 3,3,5,5-tetrasubstituted morpholin-2-ones        (NaOH), followed by dialkylation of the resulting hydroxy        carboxylate salts (NaH, alkylhalide), reduction of the ester        group (LiAlH₄), acetylation (acetylchloride, pyridine),        oxidation to the N-oxyl (peracetic acid) and alkylation of the        N-oxyl (CuCl, pentamethylethylenetriamine, 1-phenethylbromide).        3,3,5,5-Tetrasubstituted morpholin-2-ones and        3,3,5,5-tetrasubstituted morpholin-2-one N-oxyls are well known        compounds in the literature. Their preparation is described e.g.        in WO 98/44008, WO 01/23435, J. T. Lai, Synthesis 1984, 122        and S. D. Rychnovsky et al., J. Org. Chem. 1998, 63, 6363.

The following examples illustrate the invention.

A) EXAMPLES FOR THE PREPARATION OF ALKOXYAMINES

The alkoxyamines may for example be prepared from morpholinonealkoxyamines as described above. The prepared morpholinone-alkoxyamineprecursors are shown in Table 1

TABLE 1 Morpholinone-alkoxyamines No Structure 101

Reference compound as example for the general preparation 102

103

104

105

106

107

108

109

Example A1 Reference for the General Preparation:3,3,5,5-Tetramethyl-4-(1-phenyl-ethoxy)-morpholin-2-one 101

To a solution of 87.8 g (0.51 mol)3,3,5,5-tetramethyl-morpholin-2-one-N-oxyl (prepared according to J. T.Lai, Synthesis 1984, 122) in ethylbenzene (1275 ml) and water (64 ml) isadded 0.88 g (6.1 mmol) of CuBr and 1.97 g (6.1 mmol) oftetrabutylammoniumbromide at ambient temperature. The red suspension isvigorously stirred and heated to 40° C. At this temperature 150.7 ml(1.10 mol) of a 70% aqueous tert-butylhydroperoxyde solution is addedover a period of 20 min. The internal temperature rises during theaddition and is kept below 65° C. by cooling with a water-bath. Aftercomplete addition, the emulsion is stirred at 50° C. for 30 min, thencooled in an ice-bath and a solution of 137 g Na₂SO₃ in water (1000 ml)is added. The phases are separated, the organic layer is washed withwater (2×500 ml) and brine (250 ml), dried over Na₂SO₄, filtered andconcentrated under reduced pressure. The residue is recrystallized fromhexane to yield 104.8 g (74%) of the title compound as a white solid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.37-7.28 m (5H), 4.76-4.64 2q (1H),4.09 -3.87 m (2H), 1.65, 1.62, 1.35, 1.29, 1.22, 1.06, 0.85, 0.69 8s(12H), 1.48, 1.44 2d (3H).

Example A2 3,3-Diethyl-5,5-dimethyl-4-(1-phenyl-ethoxy)-morpholin-2-one102

The compound is prepared in analogy to example A1 from3,3-diethyl-5,5-dimethyl-morpholin-2-one-N-oxyl in a yield of 100%(crude) as yellow liquid.

¹H-NMR (400 MHz, CDCl₃), δ(ppm): 7.36-7.25 m (5H), 4.73-4.65 m (1H),4.04 -3.77 m (2H), 2.22-1.68 m (3H), 1.50-1.46 m (3H), 1.40-0.67 m(13H).

Example A3 5,5-Dimethyl-4-(1-phenyl-ethoxy)-3,3dipropyl-morpholin-2-one103

The compound is prepared in analogy to example A1 from5,5-dimethyl-3,3-dipropyl-morpholin-2-one-N-oxyl in a yield of 100%(crude) as slightly yellow liquid.

¹H-NMR (400 MHz, CDCl₃), δ(ppm): 7.36-7.26 (5H), 4.73-4.64 m (1H), 4.02-3.76 m (2H), 2.12-1.36 m (7H), 1.29-0.60 m (16H).

Example A4 3,5,5-Trimethyl-3-pentyl-4-(1-phenyl-ethoxy)-morpholin-2-one104

The compound is prepared in analogy to example A1 from3,5,5-trimethyl-3-pentyl-morpholin-2-one-N-oxyl in a yield of 100%(crude) as yellow liquid.

¹H-NMR (400 MHz, CDCl₃), δ(ppm): 7.34-7.25 m (5H), 4.73-4.62 m (1H),4.03, 3.92, 3.82, 3.70 4d (2H), 1.89-0.61 m (21H).

Example A52,2-Dimethyl-1-(1-phenyl-ethoxy)-4-oxa-1-aza-spiro[5.5]undecan-5-one 105

The compound is prepared in analogy to example A1 from2,2-Dimethyl-4-oxa-1-aza-spiro[5.5]undecan-5-one-N-oxyl in a yield of81% after crystallization as white solid.

M.p.: 98-102° C.

Example A62,2-Dimethyl-1-(1-phenyl-ethoxy)-4-oxa-1-aza-spiro[5.6]dodecan-5-one

The compound is prepared in analogy to example A1 from2,2-Dimethyl-4-oxa-1-aza-spiro[5.6]dodecan-5-one-N-oxyl in a yield of89% after crystallization as white solid.

M.p.: 88-90° C.

Example A7 3,5,5-Trimethyl-3-phenyl-4-(1-phenyl-ethoxy)-morpholin-2-one107

To 18.3 g (78 mmol) 3,5,5-trimethyl-3-phenyl-morpholin-2-one-N-oxyl(prepared according to S. D. Rychnovsky et al., J. Org. Chem. 1998, 63,6363), 12.0 g (117 mmol) CuCl and 25.0 ml (117 mmol)pentamethyl-diethlenetriamine, toluene (150 ml) is added. The greensuspension is stirred and a solution of 11.0 ml (78 mmol) of1-phenylethylbromide in toluene (50 ml) is slowly added during a periodof 2 h. After complete addition, the suspension is stirred for 20 h,then filtered over Hyflo, washed with 1M HCl solution (2× 70 ml), water(70 ml) and brine (70 ml), dried over Na₂SO₄, filtered and concentratedunder reduced pressure. 25.7 g (97%) of the title compound is obtainedas a slightly yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.70 d (1H), 7.54 d (1H), 7.39-7.20 m(7 H), 4.57, 4.51 2q (1H), 4.13, 3.93, 3.89, 3.70 4d (2H), 1.93, 1.66,1.37, 1.36, 1.20, 0.62 6s (9H), 1.51, 1.27 2d (3H).

Example A83-Ethyl-5,5-dimethyl-3-phenyl-4-(1-phenyl-ethoxy)-morpholin-2-one 108

The compound is prepared in analogy to example A7 from3-ethyl-5,5-dimethyl-3-phenyl-morpholin-2-one-N-oxyl in a yield of 95%as yellow liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.70-7.16 m (10H), 5.24-5.08,4.85-4.80 2m (1H), 3.99-3.50 m (2H), 2.45-0.57 m (14H).

Example A93-(4-Chloro-phenyl)-3,5,5-trimethyl-4-(1-phenyl-ethoxy)-morpholin-2-one

The compound is prepared in analogy to example A7 from3,5,5-trimethyl-3-(4-chloro)phenyl-morpholin-2-one-N-oxyl in a yield of78% as yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.64 d (1H), 7.41-7.18 m (8H),4.55-4.45 m (1H), 4.16, 3.98, 3.89, 3.74 4d (2H), 1.93, 1.68 2s (3H),1.47, 1.25 2d (3H), 1.37, 1.36 2s (3H), 1.20, 0.68 2s (3H).

The prepared alkoxyamine-diols according to formula Ia and Ib are shownin table 2. They are prepared starting from the compounds 101 to 109.

TABLE 2 Alkoxyamine-diols according to formula (Ia) and (Ib). NoStructure 201

reference: not within the scope of the invention 202

203

204

205

206

207

208

209

Example A102-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-methyl-propan-1-ol201

To a suspension of 2.93 (75 mmol) LiAlH₄ in THF (100 ml) is slowly addedat 0-10° C. a solution of 13.9 g (50 mmol) of compound 101 in THF (50ml). After complete addition, the suspension is heated to reflux andkept at this temperature for 5 h. The mixture is cooled in an ice-bathand saturated NH₄Cl-solution (25 ml) is added carefully. EtOAc (500 ml)and water (100 ml) is added, the phases separated and the organic layerwashed with water (100 ml) and brine (100 ml), dried over Na₂SO₄,filtered and concentrated under reduced pressure to yield 13.2 g (94%)of the title compound as a white solid.

M.p.: 79-81° C.

Example A112-Ethyl-2-[(2-hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-butan-1-ol202

The compound is prepared in analogy to example A10 from compound 102 ina yield of 73% after crystallization as white solid.

M.p.: 65-69° C.

Example A122-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-propyl-pentan-1-ol203

The compound is prepared in analogy to example A10 from compound 103 ina yield of 83% after crystallization as white solid. M.p.: 88-92° C.

Example A132-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-methyl-heptan-1-ol204

The compound is prepared in analogy to example A10 from compound 104 ina yield of 71% as yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.39-7.26 m (5H), 4.83-4.75 m (1H),3.79 -2.50 m (6H), 1.85-0.83 m (22H).

Example A142-[(1-Hydroxymethyl-cyclohexyl)-(1-phenyl-ethoxy)-amino]-2-methyl-propan-1-ol205

The compound is prepared in analogy to example A10 from compound 105 ina yield of 77% after crystallization as white solid.

M.p.: 84-86° C.

Example A152-[(1-Hydroxymethyl-cycloheptyl)-(1-phenyl-ethoxy)-amino]-2-methyl-propan-1-ol206

The compound is prepared in analogy to example A10 from compound 106 ina yield of 67% after crystallization as white solid.

M.p.: 68-72° C.

Example A162-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-propan-1-ol207

The compound is prepared in analogy to example A10 from compound 107 ina yield of 89% as yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.54-7.17 m (10H), 5.07, 5.00 2q (1H),4.02 -2.15 m (6H), 1.78, 1.67, 1.25, 1.03, 0.64, 0.56 6s (9H), 1.70,1.62 2d (3H).

Example A172-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-butan-1-ol208

The compound is prepared in analogy to example A10 from compound 108 ina yield of 71% after crystallization as white solid.

M.p.: 94-104° C.

Example A182-(4-Chloro-phenyl)-2-[(2-hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-propan-1-ol209

The compound is prepared in analogy to example A10 from compound 109 ina yield of 84% as yellow resin.

MS (DEP(CI)): MH⁺=378

The prepared unsymmetrically substituted open chain alkoxyaminederivatives are shown in table 3 together with their amine and nitroxideprecursors.

TABLE 3 No Structure 301

302

303

304

305

306

307

308

Example A19 Acetic Acid2-(2-benzyloxy-1,1-dimethyl-ethylamino)-2-phenyl-propyl Ester 301

The amine 301 is prepared according to the following scheme:

To a suspension of 183.8 g (2.0 mol) 2-amino-2-methylpropanol, 239 ml(2.0 mol) acetophenone, and 123.7 g (3.0 mol) NaOH in1,2-dimethoxyethane (500 ml) is slowly added 80.9 ml (1.0 mol)chloroform at 0-5° C. (ice-bath) over a period of 4.5 h. After completeaddition, the temperature is raised slowly to ambient temperature andthe brown suspension stirred overnight. Water (1 L) is added(exothermic), then tert-butylmethylether (1 L). Stirring is continuedfor 1 h, then the mixture transferred into a separation funnel, waterand tert-butylmethylether added until the phases separate. The aqueousphase is evaporated to dryness and further dried under high vacuum toyield 151 g of a brown solid. The solid is suspended in CH₂Cl₂ (500 ml),stirred for 30 min, then filtered and dried to yield 79.9 g (31%) of thesodium salt A as beige solid.

To a suspension of 73.6 g (300 mmol) of the sodium salt A is added atroom temperature 24.0 g (600 mmol) of a ca. 60% sodium hydridedispersion in oil. After stirring for 1 h 75.9 ml (660 mmol)benzylbromide is slowly added (exothermic, internal temperature is keptbelow 40° C. by cooling in a water-bath). After complete addition themixture is stirred for 1 h, another 25.0 ml (217 mmol) benzylbromide areadded, stirring continued for 1 h, another 15.0 ml (130 mmol)benzylbromide added, and stirring continued for another 2.5 h. Thereaction mixture is carefully hydrolyzed, toluene (500 ml) is added andwashed with water (2×250 ml) and brine (250 ml), dried (Na₂SO₄),filtered and evaporated. Side products are removed by distillation (0.1mbar, 170° C. bath temperature) to yield 92.4 g (74%) of thedibenzylated compound as a brown liquid. A solution of 30.0 g (71.8mmol) of this in THF (15 ml) is slowly added to a suspension of LiAlH₄in THF (150 ml), maintaining the internal temperature below 20° C. bycooling (ice-bath). After complete addition, the reaction mixture isheated to reflux for 2.5 h, then cooled to 0° C. (ice-bath) andcarefully hydrolyzed. EtOAc (250 ml) is added, the organic phase washedwith water (2×100 ml), the aqueous phases extracted with EtOAc (250 ml),the combined organic phases washed with brine (100 ml), dried (Na₂SO₄),filtered and evaporated. Benzylalcohol is removed by distillation (0.1mbar, 140° C. bath temperature) to yield 22.5 g (71.8 mmol; 100%) of thereduced compound as a brown liquid. This is dissolved in CH₂Cl₂ (100ml), 7.0 ml (86.1 mmol) pyridine added, then 6.10 ml (86.1 mmol) ofacetylchloride slowly added (exothermic, temperature is kept below 30°C. by cooling in a water bath). After complete addition, the solution isstirred at ambient temperature for 16 h, washed with 1M K₂CO₃ solution(100 ml) and brine (100 ml), dried (Na₂SO₄), filtered and evaporated toyield 26.35 g (103%) compound 301 as brown liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.56-7.54 d (2H), 7.35-7.20 m (8H),4.46 s (2H), 3.98 s (2H), 3.20 d (1H), 3.08 d (1H), 2.19 br s (1H), 1.96s (3H), 1.63 s (3H), 0.90 s (3H), 0.89 s (3H).

Example A20 Acetic Acid2-(2-benzyloxy-1,1-dimethyl-ethylamino)-2-phenyl-butyl ester 302

The compound is prepared in analogy to example A19 using propiophenoneinstead of acetophenone. Colorless liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.45 m (2H), 7.35-7.20 m (8H),4.58-4.47 m (4H), 3.08 s (2H), 2.04 s (3H), 1.85-1.76 m (2H), 0.92 s(3H), 0.81 s (3H), 0.62 t (3 H).

Example A21 Acetic Acid2-(2-benzyloxy-1,1-dimethyl-ethylamino)-2-phenyl-propyl ester-N-oxyl 303

To a solution of 26.4 g (71.8 mmol) of 301 in toluene (70 ml) is addedat the same time a 30% aq. NaOH solution (30 ml) and 23.2 ml (140 mmol)of a 40% solution of peracetic acid in acetic acid (exothermic, internaltemperature is kept below 20° C. by cooling in an ice-bath). Aftercomplete addition, the emulsion is stirred at ambient temperature for1.5 h, filtered over hyflo, the organic phase washed with 20% aq. Na₂SO₃solution (2×50 ml), water (50 ml) and brine (50 ml), dried (Na₂SO₄),filtered and evaporated. The residue is purified by flash chromatographyover silicagel (hexane/EtOAc 5:1) to give 10.9 g (41%) of the titlecompound as orange solid.

M.p.: 42-49° C. MS (DEP(CI)): MH⁺371.

Example A22 Acetic Acid2-(2-benzyloxy-1,1-dimethyl-ethylamino)-2-phenyl-butyl ester-N-oxyl 304

The compound is prepared in analogy to example A21 from compound 302 ina yield of 83% as brown liquid.

MS (DEP(CI)): MH⁺=385.

Example A23 Acetic Acid2-[(2-benzyloxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-propylEster 305

The compound is prepared in analogy to example A7 from compound 303 in ayield of 48% as yellowish liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.56-7.13 m (15H), 4.97/4.93 2q (1H),4.50, 4.47, 4.29, 4.02, 3.67, 3.55, 3.43, 3.16, 2.94, 2.62 10d (5H),4.03 s (1H), 1.79, 1.74 2s (3H), 1.61-1.53 2d+s (4.5H), 1.43, 1.22,1.05, 0.81, 0.61 5s (7.5H).

Example A242-[(2-Benzyloxy-1,1-dimethyl-ethyl)1-phenyl-ethoxy)-amino]-2-phenyl-propan-1-ol306

A solution of 15.3 g (32 mmol) of compound 305 in diethylether (35 ml)is slowly added to a suspension of 1.26 g (32 mmol) LiAlH₄ indiethylether (95 ml). The internal temperature is kept below 10° C. bycooling with an ice-bath. After complete addition, stirring is continuedat room temperature for 1.5 h. The mixture is cooled to 0° C. andcarefully hydrolyzed. The suspension is filtered, the organic phasewashed with water (50 ml) and brine (100 ml), dried (Na₂SO₄), filtratedand evaporated. The residue is purified by flash chromatography oversilicagel (hexane/EtOAc 8:1) to give 5.42 g (40%) of the title compoundas yellowish liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.62-7.16 m (15H), 5.09, 5.00 2q (1H),4.51 AB (1H), 4.05 AB (1H), 4.04, 3.44, 3.09, 2.94 4dd (3H), 3.60, 2.682d (1H), 2.54-2.51, 2.26-2.20 2m (1H), 1.77, 1.55, 1.18, 1.05, 0.82,0.70 6s (9H), 1.66, 1.54 2d (3H).

Example A25 Acetic Acid2-[(2-benzyloxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-butylEster 307

The compound is prepared in analogy to example A7 from compound 304 in ayield of 70% as yellowish liquid.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.62-7.16 m (15H), 4.97-0.25 m (24H).

Example A262-[(2-Benzyloxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-butan-1-ol308

The compound is prepared in analogy to example A24 from compound 307 ina yield of 87% as colorless resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.562-7.21 m (15H), 4.97-0.15 m (21H).

EA: required C=77.82, H=8.33, N=3.13; found: C=77.85, H=8.61, N=3.03.

The prepared symmetrically O-substituted alkoxyamines according toformula Ia and Ib are shown in table 4.

TABLE 4 No. Structure 401

402

403

404

405

406

407

408

409

410

Example A27O,O′-Di-(2-Methoxybenzoyl)-(2-Ethyl-2-[(2-hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-butan-1-ol}401

To a solution of 4.64 g (15 mmol) of compound 202 in CH₂Cl₂ (45 ml) isadded 3.60 ml (45 mmol) pyridine. 5.0 ml (36 mmol)2-methoxybenzoylchloride is slowly added while keeping the internaltemperature at ambient temperature by cooling with a water-bath. Aftercomplete addition, 0.18 g (1.5 mmol) dimethylaminopyridine is added andthe mixture is stirred for 70 h. The resulting yellow suspension isdiluted with CH₂Cl₂ (150 ml), the organic layer washed with 1M HCl (50ml), water (50 ml) and brine (50 ml), then dried over Na₂SO₄, filteredand concentrated under reduced pressure. The residue is purified byflash chromatography over silicagel (hexane/EtOAc 3:1) to give 6.94 g(80%) of the title compound as yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.93-7.88 m (1H), 7.84-7.79 m (1H),7.51 -7.41 m (2H), 7.31-7.23 m (5H), 7.00-6.90 m (4H), 4.84 m (1H),4.66-4.05 6d (3H), 3.91 -3.86 m (7H), 1.94-1.60 m (4H), 1.58-1.56 m(3H), 1.52, 1.42, 1.34, 1.24 4s (6H), 1.11, 1.02, 0.93, 0.79 4t (6 H).

Example A28O,O′-Di-(Thiophene-2-carbonyl)-{2-ethyl-2-[(2-hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-butan-1-ol}402

The compound is prepared in analogy to example A27 from compound 202 and2-thiophene-carboxylic acid chloride in a yield of 78% as yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.88-7.72 m (2H), 7.60-7.51 m (2H),7.31 -7.24 m (5H), 7.16-7.05 m (2H), 4.85-4.79 m (1H), 4.65-3.72 8d(4H), 1.96-1.60 m (4H), 1.55 d (3H), 1.51, 1.42, 1.35, 1.18 4s (6H),1.13, 1.08, 0.95, 0.81 4t (6H).

Example A29O,O′-Di-(2-Methoxybenzoyl)-{2-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-propyl-penta-1-ol}403

The compound is prepared in analogy to example A27 from compound 203 and2-methoxybenzoyl chloride in a yield of 87% as colorless resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.93-7.81 m (2H), 7.51-7.44 m (2H),7.29 -7.22 m (5H), 7.01-6.93 m (4H), 4.85-4.77 m (1H), 4.66-4.03 m (3H),3.91-3.83 m (7H), 1.88-1.14 m (17H), 0.91-0.61 m (6H).

Example A30O,O′-Di-(2-Methylthiobenzoyl)-{2-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-Phenyl-ethoxy)-amino]-2-Propyl-Pentan-1-ol}404

The compound is prepared in analogy to example A27 from compound 203 and2-(methylthio)benzoyl chloride in a yield of 71% as slightly yellowresin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 8.18-7.96 m (2H), 7.52-7.44 m (2H),7.30 -7.10 m (9H), 4.82-3.84 m (5H), 2.46-2.44 m (6H), 1.84-1.05 m(17H), 0.93-0.60 m (6H).

Example A31O,O′-Di-(2-Methoxybenzoyl)-{2-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-methyl-heptan-1-ol}405

The compound is prepared in analogy to example A27 from compound 204 and2-methoxybenzoyl chloride in a yield of 84% as slightly yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.95-7.80 m (2H), 7.52-7.42 m (2H),7.32-7.20 m (5H), 7.00-6.90 m (4H), 4.84-4.82 m (1H), 4.58-3.86 m (10H),1.90-0.80 m (23H).

Example A32O,O′-Di-(2-Methylthiobenzoyl)-{2-[(1-Hydroxymethyl-cyclohexyl)-(1-phenyl-ethoxy)-amino]-2-methyl-propan-1-ol}406

The compound is prepared in analogy to example A27 from compound 205 and2-(methylthio)benzoyl chloride in a yield of 87% as colorless resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 8.16-8.02 m (2H), 7.52-7.43 m (2H),7.30-7.22 m (7H), 7.15-7.06 m (2H), 4.94-4.88 m (1H), 4.76-3.95 8d (4H),2.48-2.44 m (6H), 2.10-1.10 m (19H).

Example A33O,O′-Di-(2-Methylthiobenzoyl)-{2-[(1-Hydroxymethyl-cycloheptyl)-(1-phenyl-ethoxy)-amino]-2-methyl-propan-1-ol}407

The compound is prepared in analogy to example A27 from compound 206 and2-(methylthio)benzoyl chloride in a yield of 64% as colorless resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 8.16-7.95 m (2H), 7.51-7.42 m (2H),7.30-7.25 m (7H), 7.15-7.00 m (2H), 4.93-4.86 m (1H), 4.63-3.76 8d (4H),2.47-2.44 m (6H), 2.18-1.22 m (21H).

Example A34O,O′-Di-(2-Methoxybenzoyl)-{2-[(2-Hydroxy-1,1-dimethyl-ethyl)-(1-phenyl-ethoxy)-amino]-2-phenyl-propan-1-ol}408

The compound is prepared in analogy to example A27 from compound 207 and2-methoxybenzoyl chloride in a yield of 81% as colorless resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.91-6.77 m (18H), 5.18-3.58 (m, 11H),1.86-0.65 m (12H).

Example A35.N.-(2-Benzyloxy-1,1-dimethyl-ethyl)-.N.-(2-benzyloxy-1-methyl-1-phenyl-ethyl)-.O.-(1-phenyl-ethyl)-hydroxylamine409

To a solution of 5.0 g (14.6 mmol) of compound 207 in THF (50 ml) isadded 1.46 g (36.4 mmol) of a ca. 60% NaH dispersion in oil. Theresulting suspension is stirred at ambient temperature for 1 h, thencooled to 0° C. (ice-bath) and 3.60 ml (29.8 mmol) benzylbromide addedslowly. The temperature is slowly raised to ambient temperature and thereaction mixture stirred for 46 h, then again cooled to 0° C. andhydrolyzed. Toluene (100 ml) is added, the organic phase washed withwater (2×100 ml) and brine (100 ml), dried (Na₂SO₄), filtrated andevaporated. The residue is purified by flash chromatography oversilicagel (hexane/EtOAc 20:1) to give 2.81 g (37%) of the title compoundas yellow resin.

¹H-NMR (400 MHz, CDCl₃), δ (ppm): 7.66-6.69 m (20H), 4.96, 4.88 2q (1H),4.56 -2.57 m (9H), 1.74-0.47 m (12H).

Example A36.N.-(2-Benzyloxy-1,1-dimethyl-ethyl)-.N.-(2-benzyloxy-1-ethyl-1-phenyl-ethyl)-.O.-(1-phenyl-ethyl)-hydroxylamine410

To a solution of 7.15 g (20 mmol) of compound 208 in toluene 100 ml) isadded 2.0 g (50 mmol) of a ca. 60% NaH dispersion in oil at 0° C. Theresulting suspension is stirred at ambient temperature for 1 h, thenagain cooled to 0° C. (ice-bath) and 5.10 ml (42 mmol) benzylbromideadded slowly. The temperature is slowly raised to ambient temperature.After 4 h DMF (50 ml) is slowly added (exothermic!). The reactionmixture is stirred overnight, then again cooled to 0° C. and hydrolyzed.Toluene (100 ml) is added, the organic phase washed with water (2×100ml) and brine (100 ml), dried (Na₂SO₄), filtrated and evaporated. Theresidue is purified by flash chromatography over silicagel (hexane/EtOAc20:1) to give 9.4 g (87%) of the title compound as yellow resin. ¹H-NMR(400 MHz, CDCl₃), δ (ppm): 7.67-6.70 m (20H), 4.96-4.70 m (1H),4.56-1.85 m (11H), 1.53-0.40 m (12H).

B) EXAMPLES FOR POLYMERIZATIONS

General Remarks:

Styrene (Merck), methylmethacrylate (MMA, Merck), n-butylacrylate(Merck) and tert-butylbenzene (Aldrich) are distilled over a Vigreuxcolumn under vacuum, shortly before being used. Acrylonitrile is used asobtained from Aldrich.

To remove oxygen, the polymerization reaction mixtures are degassed inthree consecutive freeze-thaw-cycles and then purged with argon ornitrogen before polymerization. The reaction mixtures are thenpolymerized under argon/nitrogen atmosphere. The temperatures given arebath-temperatures.

At the start of the polymerization reaction, all starting materials arehomogeneously dissolved.

Unreacted monomer is removed from the polymer by heating at a pressureof torr until constant weight is achieved. Conversion is determined byweighing the remaining polymer and subtracting the weight of theinitiator. The statistical copolymers (Sty/AN) are precipitated withmethanol, dryed at 40° C. and 1 torr until constant weight is achieved.Conversion is determined by weighing the residual.

The styrene/acrylonitrile copolymerization is carried out in a Buchiminiclave drive bmc dr (200 ml glass reactor vessel having followingfeatures: reverse bursting disc 10 bar; temperature and pressurecontrol; propeller stirrer (3 arms): torque 75 Ncm; speed 250 rpm(max.); temperature 250° C. (max.); pressure rating 100 bar (max.);material of closing cap 1.4435 Hastelloy C22; material of bearingsPFTE/graphite; stirrer shaft 8 mm.

Characterization of the polymers is carried out by GPC (Gel PermeationChromatography).

GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS. Tetrahydrofuran(THF) is used as a solvent and is pumped at 1 m/min. Two chromatographycolumns are put in series: type PIgel 5 μm mixed-C of POLYMERINSTRUMENTS, Shropshire, UK. Or by a Hewlett Packart HP 1090 LC (columnPSS 1, length 60 cm. Elution is done with tetrahydrofurane (THF), rate1m/min, concentration 10 mg polymer in 1 ml THF, Measurements areperformed at 40° C. The columns are calibrated with low polydispersitypolystyrenes having Mn from 200 to 2 000 000 Dalton. Detection iscarried out using a RI- and UV-detection. The polydispersity iscalculated from M_(n) (g/mol) and M_(w) (g/mol) as PD=M_(w)/M_(n).

Polymerization of Styrene:

Example B1 Polymerization with 1 mol % of Compound 204 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed1.47 g (4.35 mmol) of compound 204 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 28.4g (63%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=7930, Mw=10590, PD=1.34

Example B2 Polymerization with 1 mol % of Compound 205 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed1.40 g (4.35 mmol) of compound 205 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 21.7 g (48%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=5130, Mw=6180, PD=1.20

Example B3 Polymerization with 0.1 mol % of Compound 205 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed0.14 g (0.44 mmol) of compound 205 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 12.6 g (28%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=27350, Mw=34750, PD=1.27

Example B4 Polymerization with 1 mol % of Compound 207 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed1.49 g (4.35 mmol) of compound 207 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 30.7 g (68%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=7520, Mw=9300, PD=1.24

Example B5 Polymerization with 1 mol % of Compound 208 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed1.56 g (4.35 mmol) of compound 208 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 3 h. Theresidual monomer is removed under high vacuum at 70° C. 44.6 g (95%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=10000, Mw=16400, PD=1.63

Example B6 Polymerization with 0.1 mol % of Compound 208 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed0.156 g (0.435 mmol) of compound 208 and 45.3 g (435 mmol) of styreneand degassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 17.0 g (37%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=46300, Mw=74000, PD=1.60

Example B7 Polymerization with 1 mol % of Compound 209 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed1.96 g (4.35 mmol) of compound 209 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 34.9 g (73%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=9700, Mw=12100, PD=1.25

Example B8 Polymerization with 1 mol % of Compound 306 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 1.89 g(4.35 mmol) of compound 306 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 100° C. for 5 h. Theresidual monomer is removed under high vacuum at 40° C. 42.5 g (94%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=10000, Mw=11600, PD=1.27

Example B9 Polymerization with 1 mol % of Compound 307 at 75°C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer, are placed2.13 g (4.35 mmol) of compound 307 and 45.3 g (435 mmol) of styrene anddegassed. The clear solution is then stirred at 75° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 19.3 g (38%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=3130, Mw=5010, PD=1.60

Example B10 Polymerization with 1 mol % of Compound 308 at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 1.95 g(4,36 mmol) of compound 308 and 45.45 g (436 mmol) of styrene are placedand degassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 44.5 g (94%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=12050, Mw=14890, PD=1.24

Example B11 Reinitiation of Polymer B10 with MMA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.50 g ofpolymer B10 (Mn=12050) and 15.0 g (150 mmol) of MMA are placed anddegassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 2.99 g (19.9%)of the monomer is converted and a colorless foam is obtained.

Mn=46590, Mw=85150, PD=1.8

Example B12 Polymerization with 1 mol % of Compound 401 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.51 g(4.35 mmol) of compound 412 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 22.5 g (50%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=8610, Mw=10990, PD=1.28

Example B13 Polymerization with 0.1 mol % of Compound 401 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 0.25 g(0.44 mmol) of compound 412 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 19.3 g (43%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=42800, Mw=56400, PD=1.32

Example B14 Polymerization with 1 mol % of Compound 408 at 100° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.67 g(4.36 mmol) of compound 419 and 45.4 g (436 mmol) of styrene are placedand degassed. The clear solution is then stirred at 100° C. for 6 h. Theresidual monomer is removed under high vacuum at 70° C. 24.2 g (53%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=5520, Mw=7430, PD=1.35

Example B15 Polymerization with 1 mol % of Compound 208 at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 1.56 g(4.35 mmol) of compound 306 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 20.4 g (42%) ofthe monomer is converted and a slightly yellow foam is obtained.

Mn=4200, Mw=5160, PD=1.23

Example B16 Polymerization with 1 mol % of Compound 208 at 85° C. withadditional initiator

In a 100 ml Schlenck-flask with stopper and magnetic stirrer are placed1.56 g (4.35 mmol) of compound 306, 0.105 g (0.435 mmol) ofbenzoylperoxide, and 45.3 g (435 mmol) of styrene and degassed. Theclear solution is then stirred at 85° C. for 6 h. The polymer isdissolved in CH₂Cl₂ (50 ml) and precipitated from 500 ml MeOH. Theprecipitation is repeated and the resulting white powder dried underhigh vacuum to yield 34.5 g (72%) of polymer.

Mn=6890, Mw=9070, PD=1.32

Example B17 Reinitiation of Polymer B16 at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.50 g ofpolymer B16 (Mn=6890) and 10.0 g (96 mmol) of styrene are placed anddegassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 3.09 g (31%) ofthe monomer is converted and a colorless foam is obtained.

Mn=13900, Mw=23300, PD=1.67

Example B18 Polymerization with 0.25 mol % of Compound 410 at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 0.59 g(1.10 mmol) of compound 410 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 9.20 g (18.9%)of the monomer is converted and a colorless foam is obtained.

Mn=11590, Mw=14990, PD=1.29

Example B19 Reinitiation of Polymer B17 with n-BuA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.50 g ofpolymer B17 (Mn=11590) and 15.0 g (117 mmol) of n-butylacrylate (n-BuA)are placed and degassed. The clear solution is then stirred at 85° C.for 6 h. The residual monomer is removed under high vacuum at 40° C.10.1 g (67.3%) of the monomer is converted and a colorless foam isobtained.

Mn=146600, Mw=259600, PD=1.8

Example B20 Polymerization with 1.0 mol % of Compound 410 at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.35 g(4.37 mmol) of compound 410 and 45.3 g (435 mmol) of styrene are placedand degassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 24.57 g (48.9%)of the monomer is converted and a colorless foam is obtained.

Mn=4340, Mw=5600, PD=1.29

Example B21 Reinitiation of Polymer B19 with MMA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.50 g ofpolymer B19 (Mn=4340) and 15.0 g (150 mmol) of MMA, are placed anddegassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 5.69 g (37.9%)of the monomer is converted and a colorless foam is obtained.

Mn=14780, Mw=30510, PD=2.1 Polymerization of n-butyl acrylate:

Example B22 Polymerization with 1.5 mol % of Compound 208 at 120° C.

In a 25 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 0.418 g (1.17 mmol) of compound 208 and 10.0 g (78.0mmol) of n-butylacrylate are mixed and degassed. The clear solutionobtained is heated under argon to 120° C. and polymerization is carriedout during 5 h. The remaining monomer is removed by evaporation underhigh vacuum at 80° C. 8.0 g (80%) of the initial monomer have reacted. Aclear colorless viscous fluid is obtained.

Mn=5150, Mw=8040, PD=1.56

Example B23 Polymerization with 1.5 mol % of Compound 208 at 100° C.

In a 25 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 0.418 g (1.17 mmol) of compound 208 and 10.0 g (78mmol) of n-butylacrylate are mixed and degassed. The clear solutionobtained is heated under argon to 100° C. and polymerization is carriedout during 20 h. The remaining monomer is removed by evaporation underhigh vacuum at 50° C. 9.80 g (98%) of the initial monomer have reacted.A clear colorless viscous fluid is obtained.

Mn=5150, Mw=8540, PD=1.66

Example B24 Polymerization with 1.5 mol % of Compound 209 at 100° C.

In a 25 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 0.528 g (1.17 mmol) of compound 209 and 10.0 g (78mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 100° C. and polymerization is carriedout during 3 h. The remaining monomer is removed by evaporation underhigh vacuum at 50° C. 9.41 g (94%) of the initial monomer have reacted.A clear colorless viscous fluid is obtained.

Mn=7670, Mw=14300, PD=1.87

Example B25 Polymerization with 1.5 mol % of Compound 307 at 100° C.

In a 25 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 0.573 g (1.17 mmol) of compound 307 and 10.0 g (78mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 100° C. and polymerization is carriedout during 3 h. The remaining monomer is removed by evaporation underhigh vacuum at 50° C. 7.22 g (72%) of the initial monomer have reacted.A clear colorless viscous fluid is obtained.

Mn=5340, Mw=9290, PD=1.74

Example B26 Reinitiation of Polymer B24 at 100° C.

In a 25 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 2.50 g of poly-butylacrylate B24 and 10 g (96 mmol) ofstyrene are mixed and degased. The clear solution obtained is heatedunder argon to 100° C. and polymerization is carried out during 6 h. Theremaining monomer is removed by evaporation under high vacuum at 40° C.4.88 g (49%) of the initial monomer have reacted. A clear colorlessviscous fluid is obtained.

Mn=32600, Mw=51900, PD=1.59

Example B27 Polymerization with 0.25 mol % of Compound 410 at 85° C.

In a Schlenck-flask 0.59 g (1.1 mmol) of compound 410 and 55.9 g (436mmol) n-BuA are dissolved in 100 ml tert-butylbenzene and degassed. Theclear solution obtained is heated under argon to 85° C. andpolymerization is carried out during 6 h. The remaining monomer and thesolvent are removed by evaporation under vacuum at 40° C. 31.1 g (55.7%)of the initial monomer have reacted. A clear colorless vicous fluid isobtained.

Mn=72740, Mw=133400, PD=1.8

Example B28 Reinitiation of Polymer B27 with MMA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 2.50 g ofpolymer B27 (Mn=72740) and 15.0 g (150 mmol) of MMA are placed anddegassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under vacuum at 40° C. 11.6 g (77.0%) of themonomer is converted and a colorless solid is obtained.

Mn=125300, Mw=207000, PD=1.7

Statistical Copolymers with Styrene (sty)/Acrylonitrile (AN)

Example B29 Polymerization of Sty/AN (3:1) with 0.25% mol % of Compound410

In the autoclave, equipped with a thermometer and a magnetic stirrer, 75g (720 mmol) styrene and 25 g (471 mmol) acrylonitrile are mixed andstirred with 500 U/min. After addition of 1.6 g (3.0 mmol) of compound410 the homogenous solution is cooled in an ice bath and degassed withargon for 30 min. The solution is then heated to 85° C. andpolymerization is carried out during 6 h. After cooling down to roomtemperature the statistical polymer is precipitated in methanol anddried in a vacuum oven at 40° C. The polymer is obtained with 42.2%conversion as a white solid.

Mn=21630, Mw=28620, PD=1.3

Example B30 Polymerization of sty/AN (1:1) with 0.25% mol % of Compound410

In the autoclave, equipped with a thermometer and a magnetic stirrer, 50g (480 mmol) styrene and 50 g (942 mmol) acrylonitrile are mixed andstirred with 500 U/min. After addition of 1.9 g (3.5 mmol) of compound410 the homogenous solution is cooled in an ice bath and degassed withargon for 30 min. The solution is then heated to 85° C. andpolymerization is carried out during 6 h. After cooling down to roomtemperature the statistical polymer is precipitated in methanol anddried in a vacuum oven at 40° C. The polymer is obtained with 31.1%conversion as a white solid.

Mn=15730 Mw=21920, PD=1.4

Example B31 Polymerization of sty/AN (1:3) with 0.25% mol % of Compound410

In the autoclave, equipped with a thermometer and a magnetic stirrer, 25g (240 mmol) styrene and 75 g (1414 mmol) acrylonitrile are mixed andstirred with 500 U/min. After addition of 2.2 g (4.1 mmol) of compound410 the homogenous solution is cooled in an ice bath and degassed withargon for 30 min. The solution is then heated to 85° C. andpolymerization is carried out during 6 h. After cooling down to roomtemperature the statistical polymer is precipitated in methanol anddried in a vacuum oven at 40° C. The polymer is obtained with 17.1%conversion as a white solid.

Mn=8730, Mw=11930, PD=1.4

Example B32 Reinitiation of Polymer B29 with Styrene at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 1.25 g ofstatistical polymer B29 (Mn=21630) and 7.5 g (72 mmol) of styrene areplaced and degassed. The clear solution is then stirred at 85° C. for 6h. The residual monomer is removed under high vacuum at 70° C. 1.11 g(14.8%) of the monomer is converted and a colorless solid is obtained.

Mn=31120, Mw=43680, PD=1.4

Example B33 Reinitiation of Polymer B30 with n-BuA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 1.25 g ofstatistical polymer B30 (Mn=15730) and 7.5 g (58.5 mmol) of n-BuA areplaced and degassed. The clear solution is then stirred at 85° C. for 6h. The residual monomer is removed under high vacuum at 40° C. 6.88 g(91.8%) of the monomer is converted and a colorless solid is obtained.

Mn=207700, Mw=441100, PD=2.1

Example B34 Reinitiation of Polymer B31 with MMA at 85° C.

In a 100 ml Schlenck-flask with stopper and magnetic stirrer 0.51 g ofstatistical polymer B31 (Mn=8730) and 3.0 g (30 mmol) of MMA are placedand degassed. The clear solution is then stirred at 85° C. for 6 h. Theresidual monomer is removed under high vacuum at 40° C. 1.93 g (64.3%)of the monomer is converted and a colorless solid is obtained.

Mn=67350, Mw=91580, PD=1.4

1. A compound of formula Ib or Ic

wherein Y is O or NR₁₀₁ and R₁₀₁ is H or C₁-C₁₈alkyl or R₇ and/or R₈ andR₁₀₁ together with the nitrogen atom to which they are bound form a 5 or6 membered heterocyclic ring; R₁, R₂ and R₃ independently are benzyl,C₁-C₁₈alkyl, C₂-C₁₈alkenyl which are unsubstituted or substituted by OHor by a group —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by atleast one O atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkylor C₆-C₁₀aryl; or R₁ and R₂ together with the carbon atom to which theyare bound form a C₅-C₁₂cycloalkyl group; or in formula Ia R₃ and R₄together with the carbon atom to which they are bound form aC₅-C₁₂cycloalkyl group; R₅ and R₆ are independently H, C₁-C₁₈alkyl,C₂-C₁₈alkenyl, benzyl, C₅-C₁₂cycloalkyl or phenyl; R₇ and R₈independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₅-C₁₂cycloalkyl or agroup —C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl,—C(O)—C(O)—OH, —C(O)—C(O)—NH—(C₁-C₁₈alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

or —SiR_(a)R_(b)R_(c) wherein R_(a), R_(b) and R_(c) independently areC₁-C₁₈alkyl. or R₇ and R₈ are a group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen; R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ independentlyare H, OH, C₁-C₈alkoxy, C₁-C₈alkyl, SH, C₁-C₈alkylthio,—O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl, nitro, cyano, halogen or agroup NR₁₀₆R₁₀₇ wherein R₁₀₆ and R₁₀₇ independently are hydrogen,C₁-C₁₈alkyl or C₆-C₁₀aryl or together with the nitrogen atom to whichthey are bound form a 5 or 6 membered heterocyclic ring; and X isselected from the group consisting of —CH₂-aryl,

—CH₂—CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂, (C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—O—R₂₁, (C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

3-cyclohexenyl, 3-cyclopentenyl,

wherein R₂₀ is hydrogen or C₁-C₁₂alkyl; R₂₁ is C₁-C₁₈alkyl orC₂-C₁₈alkyl which is interrupted by at least one O atom or a group NR₁₀₂wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; the alkyl groupsare unsubstituted or substituted with one or more —OH, —COOH,—O(C₁-C₈alkyl), NR₁₀₆R₁₀₇ or —COR₂₀ groups wherein R₂₀, R₁₀₆ and R₁₀₇have the meanings as defined above; and the aryl groups are phenyl ornaphthyl which are unsubstituted or substituted with C₁-C₁₂alkyl,halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylthio, C₁-C₁₂alkylcarbonyl,glycidyloxy, OH, SH, —COOH or —COO(C₁-C₁₂)alkyl.
 2. A compound accordingto claim 1 wherein X is selected from the group consisting of—CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN,(CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₈alkyl)CR₂₀—C(O)-phenyl,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkoxy, (C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₂₀—C(O)—N-di(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—NH(C₁-C₈)alkyl and (C₁-C₈)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₈)alkyl.
 3. A compound according toclaim 2 wherein X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl and (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.
 4. A compound according toclaim 1 wherein Y is O.
 5. A compound according to claim 1 wherein R₁,R₂ and R₃ are C₁-C₅alkyl; R₄ is C₂-C₆alkyl; R₅ and R₆ are H; R₇ and R₈independently are H, C₁-C₁₈alkyl, allyl, benzyl, C₅-C₁₂cycloalkyl or agroup —C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—C(O)—OH,—C(S)—S—(C₁-C₁₈)alkyl,

or —SiR_(a)R_(b)R_(c) wherein R_(a), R_(b) and R_(c) independently areC₁-C₁₈alkyl, or R₇ and R₈ are a group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl; R₉, R₁₀ and R₁₁ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl; and X is as defined in claim
 1. 6. A compound of formula Ibaccording to claim 1 wherein Y is O; R₁ and R₂ are C₁-C₅alkyl, ortogether with the carbon atom to which they are bound form aC₅-C₇cycloalkyl group; R₃ is methyl, ethyl or propyl; R₅ and R₆ are H;R₇ and R₈ independently are H, C₁-C₁₈alkyl, allyl, benzyl,C₅-C₁₂cycloalkyl or a group —C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl,—C(O)—C(O)—OH, —C(S)—S—(C₁ -C₁₈)alkyl,

or —SiR_(a)R_(b)R_(c) wherein R_(a), R_(b) and R_(c) independently areC₁-C₁₈alkyl, or R₇ and R₈ are a R₁₀

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl; R₉, R₁₀ and R₁₁ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl; and X is selected from the group consisting of —CH₂-aryl,

—CH₂—CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂, (C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—O—R₂₁, (C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

3-cyclohexenyl, 3-cyclopentenyl,

wherein R₂₀ is hydrogen or C₁-C₁₂alkyl; R₂₁ is C₁-C₁₈alkyl orC₂-C₁₈alkyl which is interrupted by at least one O atom or a group NR₁₀₂wherein R₁₀₂ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; the alkyl groupsare unsubstituted or substituted with one or more —OH, —COOH,—O(C₁-C₈alkyl), NR₁₀₆R₁₀₇ or —COR₂₀ groups wherein R₂₀, R₁₀₆ and R₁₀₇have the meanings as defined above; and the aryl groups are phenyl ornaphthyl which are unsubstituted or substituted with C₁-C₁₂alkyl,halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or—COO(C₁-C₁₂)alkyl.
 7. A polymerizable composition, comprising a) atleast one ethylenically unsaturated monomer or oligomer, and b) acompound according to formula (Ib) or (Ic) according to claim
 1. 8. Aprocess for preparing an oligomer, a cooligomer, a polymer or acopolymer (block or random) by free radical polymerization of at leastone ethylenically unsaturated monomer or oligomer, which comprises(co)polymerizing the monomer or monomers/oligomers in the presence of aninitiator compound of formula (Ib) or (Ic) according to claim 1 underreaction conditions capable of effecting scission of the O—X bond toform two free radicals, the radical •X being capable of initiatingpolymerization.
 9. A process according to claim 8 wherein the scissionof the O—X bond is effected by ultrasonic treatment, heating or exposureto electromagnetic radiation ranging from γ to microwaves.
 10. A processaccording to claim 9 wherein the scission of the O—X bond is effected byheating and takes place at a temperature of between 50° C. and 160° C.11. A process according to claim 8 wherein the compound is present in anamount from 0.001 mol-% to 20 mol-%, based on the monomer or monomermixture.
 12. A polymerizable composition, comprising a) at least oneethylenically unsaturated monomer or oligomer, and b) a compoundaccording to formula (IIb) or (IIc)

wherein Y is O or NR₁₀₁ and R₁₀ is H or C₁-C₁₈alkyl or R₇ and/or R₈ andR₁₀₁, together with the nitrogen atom to which they are bound form a 5or 6 membered heterocyclic ring; R₁, R₂ and R₃ independently are benzyl,C₁-C₁₈alkyl, C₂-C₁₈alkenyl which are unsubstituted or substituted by OHor a by group —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by atleast one O atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₁-C₁₈alkylor C₆-C₁₀aryl; or R₁ and R₂ together with the carbon atom to which theyare bound form a C₅-C₁₂cycloalkyl group; or in formula Ia R₃ and R₄together with the carbon atom to which they are bound form aC₅-C₁₂cycloalkyl group; R₅ and R₆ are independently H, C₁-C₁₈alkyl,C₂-C₁₈alkenyl, benzyl, C₅-C₁₂cycloalkyl or phenyl; R₇ and R₈independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₅-C₁₂cycloalkyl or agroup —C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl,—C(O)—C(O)—OH, —C(O)—C(O)—NH—(C₁-C₁₈alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

or —SiR_(a)R_(b)R_(c) wherein R_(a), R_(b) and R_(c) independently areC₁-C₁₈alkyl, or R₇ and R₈ are group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen; and R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄independently are H, OH, C₁-C₈alkoxy, C₁-C₈alkyl, SH, C₁-C₈alkylthio,—O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl, nitro, cyano, halogen or agroup NR₁₀₆R₁₀₇ wherein R₁₀₆ and R₁₀₇ independently are hydrogen,C₁-C₁₈alkyl or C₆-C₁₀aryl or together with the nitrogen atom to whichthey are bound form a 5 or 6 membered heterocyclic ring; and c) a sourceof free radicals capable of initiating polymerization of ethylenicallyunsaturated monomers.
 13. A process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturatedmonomer/oligomer, which comprises subjecting the composition accordingto claim 12 to heat or actinic radiation.
 14. A compound of formula IIb

wherein Y is O or NR₁₀₁ and R₁₀ is H or C₁-C₁₈alkyl or R₇ and R₁₀₁together with the nitrogen atom to which they are bound form a 5 or 6membered heterocyclic ring; R₁, R₂ and R₃ independently are benzyl,C₁-C₁₈alkyl, C₂-C₁₈alkenyl which are unsubstituted or substituted by OHor a group —O—C(O)—R₁₀₂; or C₂-C₁₈alkyl which is interrupted by at leastone O atom or a group NR₁₀₂ wherein R₁₀₂ is hydrogen, C₂-C₁₈alkyl orC₆-C₁₀aryl; or R₁ and R₂ together with the carbon atom to which they arebound form a C₅-C₁₂cycloalkyl group; R₅ and R₆ are independently H,C₁-C₁₈alkyl, C₂-C₁₈alkenyl, benzyl, C₅-C₁₂cycloalkyl or phenyl; R₇ andR₈ independently are H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₅-C₁₂cycloalkyl ora group —C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—O-phenyl,—C(O)—C(O)—OH, —C(O)—C(O)—NH—(C₁-C₁₈alkyl), —C(S)—S—(C₁-C₁₈)alkyl,

or —SiR_(a)R_(b)R_(c) wherein R_(a), R_(b) and R_(c) independently areC₁-C₁₈alkyl, or R₇ and R₈ are a group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkyl,C₁-C₈alkoxy, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, —O—C(O)—(C₆-C₁₀)aryl,nitro, cyano or halogen; and R₉, R₁₀ and R₁₁, independently are H, OH,C₁-C₈alkoxy, C₀-C₈alkyl, SH, C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl,—O—C(O)—(C₆-C₁₀)aryl, nitro, cyano, halogen or a group NR₁₀₆R₁₀₇ whereinR₁₀₆ and R₁₀₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl ortogether with the nitrogen atom to which they are bound form a 5 or 6membered heterocyclic ring.
 15. A compound of formula IIb according toclaim 14 wherein Y is O; R₁ and R₂ are —CH₃, or together with the carbonatom to which they are bound form a C₅-C₇cycloalkyl group; R₃ is methyl,ethyl or propyl; R₅ and R₆ are H; R₇ and R₈ independently are H,C₁-C₁₈alkyl, allyl, benzyl, C₅-C₁₂cycloalkyl or a group—C(O)—(C₁-C₁₈)alkyl, —C(O)—O—(C₁-C₁₈)alkyl, —C(O)—C(O)—OH,—C(S)—S—(C₁-C₁₈)alkyl or —SiR_(a)R_(b)R_(c) wherein R_(a)R_(b) and R_(c)independently are C₁-C₁₈alkyl, or R₇ and R₈ are group

wherein R₁₀₃, R₁₀₄ and R₁₀₅ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl; and R₉, R₁₀ and R₁₁ independently are H, C₁-C₈alkoxy,C₁-C₈alkylthio, —O—C(O)—(C₁-C₈)alkyl, nitro, cyano, halogen orC₁-C₈alkyl.